CN103506152B - A kind of catalyst processing hydrotreated feed oil - Google Patents
A kind of catalyst processing hydrotreated feed oil Download PDFInfo
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- CN103506152B CN103506152B CN201210213656.2A CN201210213656A CN103506152B CN 103506152 B CN103506152 B CN 103506152B CN 201210213656 A CN201210213656 A CN 201210213656A CN 103506152 B CN103506152 B CN 103506152B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Process a catalyst for hydrotreated feed oil, described catalyst is primarily of the molecular sieve mixture composition of the heat-resistant inorganic oxide of 5-35 % by weight, the clay of 0-65 % by weight, the modification mesoporous silica-alumina materials of 5-50 % by weight and 15-60 % by weight; Wherein said molecular sieve mixture comprises beta-molecular sieve and MFI molecular sieve, with the weight of catalyst for benchmark, the content of described beta-molecular sieve is 10-55 % by weight, the content of described MFI molecular sieve is 5-25 % by weight, the weight ratio of described beta molecular sieve and described modified mesoporous material is 1:5-5:1, and described beta molecular sieve is not less than 1 with the ratio of the weight of MFI molecular sieve.This catalyst is used for hydrotreated feed oil and transforms, and has higher propylene and isobutene yield.
Description
Technical field
The present invention relates to a kind of catalyst processing hydrotreated feed oil, relate to a kind of catalytic cracking catalyst utilizing hydrotreated feed oil to produce propylene and butylene furtherly.
Background technology
Along with oil property is deteriorated increasingly, heavy raw oil hydrotreatment is more and more come into one's own, but hydrotreatment is unsuitable for producing the low-carbon alkene such as propylene, butylene, therefore utilizes hydrotreated feed oil to produce propylene for raw material catalytic cracking and gradually come into one's own.Different from the fcc raw material of routine, hydrotreated feed oil has higher saturation degree and H/C ratio, has more cycloalkane and the mononuclear aromatics with naphthenic ring.Current productivity of low carbon olefin hydrocarbon such as hydrotreatment oil converting propylene, butylene etc. is often not high, does not have to find to transform for Hydrogenation raw oil the catalyst producing low-carbon alkene exploitation specially.
CN101134172B discloses a kind of catalytic cracking catalyst, its contain the zeolite mixture of 1% ~ 60%, the heat-resistant inorganic oxide of 5% ~ 99% and 0 ~ 70% clay, with zeolite mixture gross weight for benchmark, in described zeolite mixture containing 1% ~ 75% by phosphorus and transition metal M modification Β zeolite, 25% ~ 99% there is the zeolite of MFI structure and the large pore zeolite of 0 ~ 74%.This catalyst can be used for hydrocarbons catalytic conversion process and produces low-carbon alkene.But this patent do not relate to hydrotreated feed oil transform produce low-carbon alkene, its for hydrotreatment oil converting propylene and isobutene productive rate not high.
CN200710179420 discloses a kind of Cracking catalyst made by the mesopore zeolite containing dehydrogenation component, its dehydrogenation component is adopt one or more in palladium, platinum, iron-cobalt-nickel, chromium, molybdenum, tungsten, vanadium, and mesopore zeolite is ZSM-5 or the ZRP Series Molecules sieve with MFI structure.This catalyst mainly for Conventional catalytic raw material produce low-carbon alkene exploitation catalyst, do not relate to improve hydrotreatment oil transform propylene and butylene productive rate, its for hydrotreatment oil converting propylene and isobutene productive rate not high.
Summary of the invention
The present inventor finds under study for action, naphthenic ring some generation open loop cracking reaction in catalytic cracking process obtained through hydrotreated lube base oil by aromatic rings in naphthenic ring such as hydrotreatment oil, transform and produce low-carbon alkene, some is fragrant fluidized dehydrogenation formation aromatic rings and other product again, this causes on the one hand mononuclear aromatics virtueization formation dicyclo and above aromatic hydrocarbons or the heavier product of formation again, make product complex distribution, institute's hydrogen supply with negative hydrogen ion form saturation of olefins, may cause productivity of low carbon olefin hydrocarbon and optionally reduces on the other hand.Prior art normally for non-Hydrogenation raw oil, does not consider that the transformation characteristics of hydrotreated feed oil is developed or optimizes for the production of the catalyst of low-carbon alkene, and when transforming for hydrogenating materials, productivity of low carbon olefin hydrocarbon is not high.Therefore, the present inventor, on the basis that lot of experiments is studied, proposes exploitation transforms the catalyst producing low-carbon alkene technical thought for Hydrogenation raw oil.
The technical problem to be solved in the present invention is to provide a kind of catalyst transforming production propylene and butylene for hydrotreatment oil, this catalyst is used for transforming containing cycloalkane and/or with the hydrotreatment oil that the mononuclear aromatics of naphthenic ring is more, has higher propylene and isobutene yield.The other technical problem that the present invention will solve is to provide the preparation method of described catalyst.
The invention provides a kind of catalyst transformed for hydrotreatment oil, take catalyst weight as benchmark, mainly comprise in the modification mesoporous silica-alumina materials of butt 5-50 % by weight, in the molecular sieve mixture of butt 15-60 % by weight, in the heat-resistant inorganic oxide of oxide basis 5-35 % by weight with the clay of butt 0-65%; Wherein said molecular sieve mixture comprises beta molecular sieve and MFI molecular sieve, and the ratio of described beta molecular sieve and the weight of described MFI molecular sieve is for being not less than 1, and the weight ratio of described beta molecular sieve and described modified mesoporous material is 1:5-5:1.
Usually, with the weight of catalyst for benchmark, in described catalyst, the content of beta molecular sieve is 10-55 % by weight, and the content of described MFI molecular sieve is 2-25 % by weight.
The weight ratio of described beta molecular sieve and MFI molecular sieve is not less than 1, is generally 1:1-12:1.
The present invention also provides a kind of preparation method of the catalyst for the conversion of hydrotreatment oil provided by the present invention, comprise being formed and comprise described molecular sieve mixture, modification mesoporous silica-alumina materials, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor, contain or catalyst slurry not argillaceous, spray-dired step.
Low-carbon alkene is produced in the cracking that catalyst provided by the invention is used for hydrotreated feed oil, and have higher propylene and butylene productive rate, have higher isobutene productive rate, in liquefied gas, the concentration of propylene and isobutene is high, and in gasoline fraction aromatic hydrocarbons, BTX ratio is higher; Can also have lower polycyclic aromatic hydrocarbons (PAH) content and paraffinicity in diesel oil and heavy oil, thus be conducive to obtaining the diesel oil that pour point is low and Cetane number is higher, total aromatics yield is lower.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of modification mesoporous silica-alumina materials prepared by embodiment 1.
Detailed description of the invention
In the present invention, low-carbon alkene refers in particular to C3-C4 alkene; Light gasoline fraction, refer to that initial boiling point is 70-85, the end point of distillation is the gasoline fraction of 140-150 DEG C.Light aromatic hydrocarbons refers to benzene, toluene, ethylbenzene and dimethylbenzene, represents benzene, toluene and dimethylbenzene with BTX.
Catalyst provided by the invention, take total catalyst weight as benchmark, be made up of the clay comprising beta molecular sieve and there is the molecular sieve mixture of MFI structure molecular sieve, the heat-resistant inorganic oxide of 5-35 % by weight and 0-65 % by weight of the modification mesoporous silica-alumina materials of 5-50 % by weight, 15-60 % by weight; Under optimum condition, the content of described modification mesoporous silica-alumina materials is 5-40 % by weight, the content of molecular sieve mixture is 15-50 % by weight, the content of heat-resistant inorganic oxide is 5-30 % by weight, the content of clay is 0-55 % by weight, the content of described beta molecular sieve is 10-45 % by weight, and be preferably 15-40 % by weight, the content of described MFI molecular sieve is 5-22 % by weight.The weight ratio of described beta molecular sieve and described MFI molecular sieve (molecular sieve also referred to as having MFI structure) is preferably 2:1-9:1, is more preferably 3:1-6:1.The weight ratio of described beta molecular sieve and described modified mesoporous material is 1:5-5:1, is preferably 1:3-2:1.Such as, described catalyst can be made up of the modification mesoporous silica-alumina materials of the binding agent of the clay of the MFI molecular sieve of the beta molecular sieve of 12-30 % by weight, 3-15 % by weight, 15-45 % by weight, 15-35 % by weight and 5-25 % by weight.
Described modification mesoporous silica-alumina materials is the mesoporous silica-alumina materials through exchanging sodium, and described modification mesoporous silica-alumina materials in the anhydrous expression formula of oxide weight is: (0-0.3) Na
2o (40-90) Al
2o
3(10-60) SiO
2.Its specific area 200-400m
2/ g, pore volume is that 0.5-2.0ml/g is preferably 1.0-2.0ml/g, and average pore size is that 5-25nm is preferably 8-15nm, and most probable pore size is 5-15nm, preferred 5-10nm.Described modification mesoporous silica-alumina materials preferably has boehmite crystal phase structure.
Modification mesoporous silica-alumina materials of the present invention can obtain according to existing method, such as obtain according to method disclosed in CN1854258A, the method is by the CN1565733A(such as mesoporous silica-alumina materials described in CN1565733A claim 1-10 or the mesoporous silica-alumina materials prepared by embodiment) said mesoporous silica-alumina materials obtains after acidification.The condition of acidification is, under room temperature to 80 DEG C, 0.1 ~ 0.3 sour aluminum ratio condition, mesoporous silica-alumina materials is contacted 0.5 ~ 3 hour with inorganic acid.One or more in described inorganic acid such as hydrochloric acid, nitric acid and sulfuric acid.
Preferred, described modification mesoporous silica-alumina materials is obtained by the method comprised the following steps:
Mesoporous silica-alumina materials without ion-exchange is mixed with water and pulls an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour usual 0.2-10 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3.The mesoporous silica-alumina materials that the method obtains has higher propylene and butylene yield.The weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is preferably 1:(6-20): (0.05-0.2), is more preferably 1:(8-15): (0.07-0.16).In the present invention, in the weight ratio without the mesoporous silica-alumina materials of ion-exchange, water and inorganic acid, the weight of the described mesoporous silica-alumina materials without ion-exchange is in its butt; The weight of described inorganic acid refers to the weight of inorganic acid component, and such as, when described inorganic acid adds fashionable with the form of aqueous hydrochloric acid solution, the weight of described inorganic acid refers to the weight of HCl in aqueous hydrochloric acid solution.In the process of the described mesoporous silica-alumina materials of preparation, the condition contacted with inorganic acid by described slurries can for conventional ion exchange conditions.Under preferable case, the temperature of described contact is 30-80 DEG C, is more preferably 40-70 DEG C; The time of described contact is 0.2-2 hour, is more preferably 0.3-1.5 hour.
In the present invention, in the weight ratio without the mesoporous silica-alumina materials of ion-exchange, water and inorganic acid, the described mesoporous silica-alumina materials weight without ion-exchange is the weight in butt.In the present invention, the weight of roasting after 1 hour under the condition of about 800 DEG C is referred in the weight of butt.
In the present invention, described inorganic acid can be the inorganic acid of various routine, such as can one or more for being selected from sulfuric acid, hydrochloric acid and nitric acid.
In the process of the described modification mesoporous silica-alumina materials of preparation, the not special requirement of the mode that described slurries are contacted with inorganic acid, inorganic acid can be joined in described slurries and carry out mixing contact, also described slurries can be added in inorganic acid and carry out mixing contact.Under preferable case, inorganic acid is joined in described slurries and carry out mixing contact.
In the present invention, described mesoporous silica-alumina materials preferably has boehmite crystal phase structure, and its X-ray diffracting spectrum as shown in Figure 1.And described modification mesoporous silica-alumina materials, in the anhydrous chemical expression of oxide weight is: (0-0.2) Na
2o(40-90) Al
2o
3(10-60) SiO
2.
In the process of the described modification mesoporous silica-alumina materials of preparation, the various mesoporous silica-alumina materials without any ion-exchange that the described mesoporous silica-alumina materials without ion-exchange can be commonly used for this area.The described mesoporous silica-alumina materials without ion-exchange can prepare according to the method for routine, and its preparation method such as can comprise: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, plastic terminal pH is 7-11; Then according to SiO
2: Al
2o
3=1:(0.6-9) weight ratio add silicon source, aging 1-10 hour at room temperature to 90 DEG C, then filters.In the present invention, the sial sediment obtained after described filtration directly can be used as the described mesoporous silica-alumina materials without ion-exchange, is used as the described mesoporous silica-alumina materials without ion-exchange after also can being carried out drying and/or roasting.Described aluminium source can be the various aluminium sources that this area routine uses, and described aluminium source such as can one or more for being selected from aluminum nitrate, aluminum sulfate or aluminium chloride.Described silicon source can be the various silicon sources that this area routine uses, and described silicon source can be such as at least one in silica gel, waterglass, sodium metasilicate, silicon tetraethyl, silica, Ludox and Silica hydrogel.Described aqueous slkali can be the various aqueous slkalis that this area routine uses, such as, can be one or more in ammoniacal liquor, potassium hydroxide solution, sodium aluminate solution and sodium hydroxide solution.
In the described process without the mesoporous silica-alumina materials of ion-exchange of preparation, although described aluminium source, silicon source and aqueous slkali suitably can be selected separately from the above-mentioned material enumerated, but, having at least in usual described aluminium source, aqueous slkali and silicon source is a kind of for containing the raw material of sodium, thus ensures that the described mesoporous silica-alumina materials without ion-exchange of so preparation has the meso-hole structure of appropriate size.
In the present invention, described without in the mesoporous silica-alumina materials of ion-exchange in the sodium content of sodium oxide molybdena for 0.5-15 % by weight.And in described catalytic cracking catalyst of the present invention, adopt in the described described mesoporous silica-alumina materials prepared without the mesoporous silica-alumina materials of ion-exchange and be generally less than 0.2 % by weight in the sodium content of sodium oxide molybdena.
In catalyst provided by the present invention, beta molecular sieve and described modified mesoporous material weight ratio be 1:5-5:1, be preferably 1:3-3:1.
In catalyst provided by the invention, the weight ratio of described beta molecular sieve and described MIF molecular sieve (molecular sieve also referred to as having MFI structure) is preferably 2-9:1, be more preferably 3-6:1, and two kinds of molecular sieve sums are the 75-100 % by weight of described molecular sieve mixture weight.Described beta molecular sieve can be Hydrogen, also can be that phosphorus and/or transition metal modified beta molecular sieves are as being through one or more the element modified beta zeolites in P, Re, Fe, Co, Ni, Cu, Mn, Zn and Sn, or be their mixture, be preferably Hydrogen beta molecular sieve, P Modification beta molecular sieve, through P and be selected from the beta molecular sieve of one or more modifications in Fe, Co, Ni and Cu one or more, the silica alumina ratio (SiO of described Beta molecular sieve
2/ Al
2o
3mol ratio) be generally 8-200, preferred 10-100.Described MFI molecular sieve is the high-silica zeolite with pentasil structure, its can for existing have in the molecular sieve of MIF structure one or more, it is such as ZSM-5 zeolite, one or more in ZRP zeolite, can be through P, Re, Fe, Co, Ni, Cu, Mn, Zn, Sn, one or more element modified ZSM-5 such as Mo and Ga and through P, Re, Fe, Co, Ni, Cu, Mn, Zn, Sn, one or more mixture in one or more element modified ZRP series zeolite such as Mo and Ga, particularly be selected from the ZRP zeolite (CN1052290A containing rare earth, CN1058382A, US5232675), phosphorous ZRP zeolite (CN1194181A, US5951963), the ZRP zeolite (CN1147420A) of phosphorous and rare earth, ZRP zeolite (the CN1211469A of phosphorous and alkaline-earth metal, CN1211470A, and phosphorous and ZRP zeolite (CN1465527A that is transition metal US6080698), CN1611299A) one or more in.Silica alumina ratio (the SiO of described MFI molecular sieve
2/ Al
2o
3mol ratio) be generally 10-300, preferred 15-150.
In catalyst provided by the invention, described molecular sieve mixture comprises beta molecular sieve and MFI molecular sieve, also can comprise other molecular sieve being no more than 25 % by weight.In described molecular sieve mixture, beta molecular sieve (beta-molecular sieve) is not less than 1:1 with the weight ratio of MFI molecular sieve, be preferably 3:1-6:1, and these two kinds of molecular sieve sums account for the 75-100 % by weight of molecular sieve mixture, other molecular sieve described is preferably clinoptilolite and/or modenite, the content 0-25 % by weight of other molecular sieve described.Preferably, described molecular sieve mixture does not contain the molecular sieve of faujasite structure, described faujasite structure molecular screen such as Y zeolite, X-type molecular sieve.Described molecular sieve mixture is preferably the mixture of beta molecular sieve and MFI structure molecular sieve or the mixture for clinoptilolite and/or modenite, beta molecular sieve and MFI structure molecular sieve, and beta molecular sieve and the weight ratio 3:1-6:1 of molecular sieve with MFI structure, in these cases, introduce described clinoptilolite, liquefied gas yield can be improved more significantly.
In catalyst provided by the invention, one or more in heat-resistant inorganic oxide conventional in the optional catalytic cracking catalyst of described heat-resistant inorganic oxide, such as be commonly used in the heat-resistant inorganic oxide in binding agent and modified additive material one or more, one or more in described binding agent such as silica, aluminium oxide, silica-alumina, phosphorus-aluminium compound; Described modified additive material such as P
2o
5, Al
2o
3.Preferred heat-resistant inorganic oxide is one or more in aluminium oxide, silica, silica-alumina, phosphorous oxides, phosphorous oxide-aluminium oxide.The binding agent introduced when these heat-resistant inorganic oxides can be derived from preparation and/or the modified material introduced when being derived from preparation, one or more in described binding agent such as aluminium oxide, hydrated alumina, Alumina gel, Ludox, Silica hydrogel, waterglass, silica-alumina gel, silicon-aluminum sol, acidification pseudo-boehmite, phosphaljel, aluminium phosphate sol and their precursor or various modifier.Described binding agent is by being purchased or preparing according to existing method, such as, the method preparation that acidification pseudo-boehmite can provide according to patent US4010116, US4206085, the method preparation that Ludox can provide according to US Patent No. 3957689, US3867308, the method preparation that aluminium phosphate sol can provide according to patent CN1008974C, CN1083512A.Preferred binding agent is one or more in boehmite, Alumina gel and phosphorus Alumina gel and/or silicon phosphorus Alumina gel.
Clay of the present invention is selected from one or more that be usually used in the clay of Cracking catalyst, such as, in kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite one or more.These clays are that those of ordinary skill in the art are known, are preferably kaolin or halloysite.In catalyst provided by the invention, the content of clay is generally 5-45 % by weight.
The preparation method of provided by the inventionization catalyst, by described modification mesoporous silica-alumina materials, clay, binding agent, molecular sieve mixture mixing making beating, obtained catalyst slurry, described catalyst slurry is carried out spraying dry, can carry out according to the preparation method of existing Cracking catalyst or auxiliary agent, such as, method in patent CN1098130A, CN1362472A, CN1727442A, CN1132898C or CN1727445A.Preferably, the preparation method of described catalyst slurry is: by described modified clay, binding agent mixing making beating, add or do not add acid, aging 30-120min is stirred at 60-80 DEG C, obtained first slurries, again the first slurries are mixed with mesoporous silica-alumina materials and mixed molecular sieve and pull an oar, obtained second slurries and catalyst slurry, carry out spraying dry to the second slurries and obtain described catalyst microspheres, preferred binding agent is one or more in boehmite, acidification pseudo-boehmite, Alumina gel, phosphorus Alumina gel, silicon-aluminum sol, Ludox and silicon phosphorus Alumina gel.Wherein, acid can also be introduced in first slurries, the consumption of acid makes the pH value stating slurries be 1-5, be preferably 1.5-4, described acid is selected from one or more of water-soluble organic acid and inorganic acid, and preferred hydrochloric acid, nitric acid, oxalic acid, phosphoric acid and carbon number are one or more in the carboxylic acid of 1-10.The solid content of preferably prepared catalyst slurry is 5 ~ 45 % by weight.
In method for preparing catalyst provided by the invention, catalyst slurry spraying dry is obtained catalyst microspheres, this catalyst microspheres can be directly used in course of reaction, also can comprise the step of the catalyst microspheres roasting obtained by spraying dry, or comprise the steps such as the catalyst microspheres washing obtained by spraying dry, dry, roasting and ammonium exchange.Described washing, drying, roasting and ammonium are exchanged for prior art, and the present invention does not have particular/special requirement.
The feedstock oil that the mononuclear aromatics that catalyst provided by the invention is applicable to contain cycloalkane and contain naphthenic ring is more, such as hydrotreatment oil contains the more paraffin-base oil material of cycloalkane with some.In described hydrotreatment oil, dicyclo and fragrant number of rings are more than the polycyclic aromatic hydrocarbon content of two preferably more than 15 % by weight, and described hydrotreatment oil wax content is preferably more than 20 % by weight, and naphthene content is not less than 30 % by weight.The condition of described catalytic cracking can with reference to existing RFCC condition, and such as reaction temperature is 450-650 DEG C, and agent weight of oil is than being 3-10, and weight (hourly) space velocity (WHSV) is 1-500h
-1, such as weight (hourly) space velocity (WHSV) 2-20h
-1.
The present invention is described further for the following examples, but therefore do not limit the present invention.
In embodiment and comparative example: beta molecular sieve solid content 95.2 % by weight, silica alumina ratio (SiO used
2/ Al
2o
3mol ratio) be 25, sodium oxide content 0.1 % by weight; ZRP-1, silica alumina ratio (SiO
2/ Al
2o
3mol ratio) be 30, Na
2o content is 0.1 % by weight, phosphorus content 1 % by weight, Re
2o
3content 2 % by weight, solid content 95 % by weight; The lattice constant of DASY0.0 molecular sieve is 2.443nm, Na
2o content is 0.85 % by weight, solid content 92.0 % by weight; Above molecular sieve is catalyst asphalt in Shenli Refinery of China Petrochemical Industry and provides product.Alumina gel is provided by catalyst asphalt in Shenli Refinery of China Petrochemical Industry, its Al
2o
3content is 21.5 % by weight, and boehmite is Shandong Aluminum Plant's industrial products, and solid content is 62.0 % by weight, and kaolin is that Suzhou China Kaolin Co., Ltd produces, and solid content is 76 % by weight.In comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In embodiments, the Na of mesoporous material used
2o, Al
2o
3, SiO
2measure with the content XRF of modified metal-oxide, (see volumes such as " Petrochemical Engineering Analysis method " (RIPP test method) Yang Cuiding, Science Press, nineteen ninety publishes)
Embodiment 1
The preparation of modification mesoporous silica-alumina materials
Be 90g Al by concentration
2o
3the Al of/L
2(SO
4)
3solution and concentration are 102g Al
2o
3/ L, Crater corrosion are the NaAlO of 1.7
2solution stream adds in continuous gel formation still, colloid generating kettle effective volume is 200ml, Al
2(SO
4)
3the flow of solution is 20ml/min, regulates NaAlO
2flow keeps plastic pH value to be 9, and gelling temperature is 55 DEG C; Collect the slurries 300ml after plastic, adding 127ml content is under agitation 60g SiO
2waterglass (modulus 3.1) aqueous solution of/L, be warming up to 80 DEG C aging 4 hours, then filter.
Be that 1:12 carries out mixing and pulls an oar with weight ratio by the sial sediment that obtains after filtering and water, in the slurries obtained after again hydrochloric acid solution being added making beating by the weight ratio of described sial sediment (butt): HCl=1:0.14, at 60 DEG C, carry out acid to sial sediment exchanges with the sodium ion removed wherein, swap time is 30 minutes, then filter, and the sediment obtained after filtration is carried out drying and roasting successively, thus obtain modification mesoporous silica-alumina materials, JK1.This mesoporous silica-alumina materials sample has boehmite crystal phase structure, and its X-ray diffraction spectral line as shown in Figure 1; Its elementary analysis weight chemistry consists of 0.06Na
2o73.8Al
2o
326.0SiO
2.Its physical and chemical performance is as shown in table 1.
Embodiment 2
Method according to implementing 1 in CN 1854258A obtains mesoporous silica-alumina materials SH-SA-1, and the present invention is designated as JK2.
Embodiment 3
The preparation process of mesoporous material JK3 is basic identical with the mesoporous silica-alumina materials SA-2 of embodiment in CN1565733A 2, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-2, namely the sial sediment after aging filtration, to mix by the weight ratio of 1:10 with water and pull an oar, again HCl solution is joined in above-mentioned slurries by the weight ratio of sediment (butt): HCl=1:0.12, at 55 DEG C, carry out acid to sial sediment exchanges with removing sodium ion wherein, swap time is 40 minutes, after filtration, obtains mesoporous material and modification mesoporous silica-alumina materials of the present invention after dry and roasting, is designated as JK3.This sample has the feature of the X-ray diffraction spectral line of curve 2 in accompanying drawing; Its elementary analysis weight chemistry consists of 0.10Na
2o58.9Al
2o
340.9SiO
2; Its physico-chemical parameter such as specific surface, pore volume lists in table 1.
Embodiment 4
The preparation process of mesoporous material JK4 is basic identical with the mesoporous silica-alumina materials SA-5 of embodiment in CN1565733A 5, just adopts sour exchange process to substitute ammonium exchange process wherein.By the intermediate sedimentation thing of SA-5, namely the sial sediment after aging filtration, to mix by the weight ratio of 1:8 with water and pull an oar, again these slurries are joined in rare HCl solution by the weight ratio of sediment (butt): HCl=1:0.15, at 50 DEG C, carry out acid to sial sediment exchanges with removing sodium ion wherein, swap time is 20 minutes, after filtration, obtains modification mesoporous silica-alumina materials after dry and roasting, is designated as JK4.This sample has the feature of the X-ray diffraction spectral line of curve 2 in accompanying drawing; Its elementary analysis weight chemistry consists of 0.05Na
2o74.2Al
2o
325.7SiO
2; Its physico-chemical parameter such as specific surface, pore volume lists in table 1.
Comparative example 1
Adopt the mesoporous silica-alumina materials SA-1 in CN1565733A, be designated as JK0, its chemical composition is
0.12Na
2O·73.7Al
2O
3·26.2SiO
2；
Table 1
Embodiment 5
(1) in 15kg decationized Y sieve water, add 7.5kg (in butt, lower same) kaolin making beating, then add 2.4kg(with Al
2o
3meter, lower same) boehmite, stir 10 minutes, with hydrochloric acid, its pH value is adjusted to 2, stir 10 minutes, stop stirring, at 70 DEG C, leave standstill aging 1 hour, add 3.6kg Alumina gel (with Al
2o
3meter, lower same), stir, obtain alumina-clay slurries;
(2) in 15kg decationized Y sieve water, 6.0kgbeta molecular sieve is added (in butt, down together), 1.5kgZRP-1(is in butt, lower same) molecular sieve, 4.0kg(in butt lower with) obtained by modification mesoporous silica-alumina materials JK1, pull an oar 30 minutes, obtain the mixed serum of molecular sieve and modified mesoporous material, these slurries are joined in alumina-clay slurries prepared by above-mentioned steps (1), stir 0.5h, obtain catalyst slurry, by the catalyst slurry spray drying forming obtained, 500 DEG C of roastings 1.5 hours, obtain catalytic cracking catalyst C1.Composition and the physical and chemical performance of C1 list in table 2.
Embodiment 6-8
According to method Kaolinite Preparation of Catalyst C2, C3 and C4 of embodiment 5, unlike the proportioning of adjustment beta and ZRP-1, its proportioning is in table 2.
Embodiment 9
Catalytic cracking catalyst is prepared according to the method in embodiment 5, difference is, replaces described mesoporous silica-alumina materials JK1 with described mesoporous silica-alumina materials JK2, and regulates beta molecular sieve and mesoporous silica-alumina materials ratio to be 4:1, thus obtained catalytic cracking catalyst C5, its concrete proportioning is in table 2.
Embodiment 10
Catalytic cracking catalyst is prepared according to the method in embodiment 5, difference is, replaces described mesoporous silica-alumina materials JK1 with described mesoporous silica-alumina materials JK3, and regulates beta molecular sieve and mesoporous silica-alumina materials ratio to be 8:5, thus obtained catalytic cracking catalyst C5, its concrete proportioning is in table 2.
Embodiment 11
Catalytic cracking catalyst is prepared according to the method in embodiment 5, difference is, replaces described mesoporous silica-alumina materials JK1 with described mesoporous silica-alumina materials JK4, and regulates beta molecular sieve and mesoporous silica-alumina materials ratio to be 1: 1, thus obtained catalytic cracking catalyst C5, its concrete proportioning is in table 2.
Comparative example 2
According to the method Kaolinite Preparation of Catalyst of embodiment 5, unlike not adding MFI structure zeolite, obtain catalyst D1, its proportioning is in table 2.
Comparative example 3
According to the method Kaolinite Preparation of Catalyst of embodiment 5, unlike, the content of MFI structure zeolite is 3:1 with the ratio of the content of beta zeolite, obtains catalyst D2, and its proportioning is in table 2.
Comparative example 4
Be prepared in catalyst according to the method for embodiment 5, unlike the use of mesoporous silica-alumina materials JK0 replacement JK2 wherein, obtain catalyst D3, its proportioning is in table 2.
Comparative example 5
Be prepared in catalyst according to the method for embodiment 4, unlike without modification mesoporous silica-alumina materials, obtain catalyst D4, its proportioning is in table 2.
Comparative example 6
By 6.8gH
3pO
4(concentration 85 % by weight) and 3.2g nitrate trihydrate copper are dissolved in the aqueous solution and 100g (butt) beta molecular sieve hybrid infusion that obtain in 90g water, and dry, gained sample is calcination process 2h at 550 DEG C, obtain about containing 4.0 % by weight P
2o
5, 4.0 % by weight CuO modification beta molecular sieve, be designated as P-Cu-beta molecular sieve.
(1) in 15kg decationized Y sieve water, add the making beating of 7.5kg kaolin, then add 2.4kg boehmite, with hydrochloric acid, its pH value is adjusted to 2, stirs, stop stirring, at 70 DEG C, leave standstill aging 1 hour, add 3.6kg (with Al
2o
3meter) Alumina gel, stir, obtain alumina-clay slurries.
(2) add in 15kg decationized Y sieve water the P-Cu-beta molecular sieve prepared by 4.5kg, 1.1kgZRP-1 molecular sieve, 1.9Kg DASY0.0 molecular sieve and, 4.0kg(butt) obtained modification mesoporous Si-Al JK1,4.0 making beating 30 minutes, obtain the mixed serum of molecular sieve and modified mesoporous material, these slurries are joined in alumina-clay slurries prepared by above-mentioned steps (1), stir 0.5h, obtain catalyst slurry, by the slurries spray drying forming then will obtained, 500 DEG C of roastings 1.5 hours, obtain catalytic cracking catalyst D5.Composition and the physical and chemical performance of D5 list in table 2.
Embodiment 12-19
Catalyst prepared by explanation is used for the reactivity worth of hydrogenation VGO.
The catalyst C1-C7 prepared by embodiment 5-11 was at 800 DEG C, with 100% steam aging 12 hours, the cracking performance of miniature fixed fluidized bed ACE reaction unit to catalyst is used to evaluate, the loadings of catalyst reactor is 9 grams, and reaction temperature is 500 DEG C, and weight (hourly) space velocity (WHSV) is 16h
-1, pass into HTVGO in the sand shown in hydrogenation VGO(table 3) and the mixture of steam, evaluate, steam accounts for 25 % by weight of hydrogenation VGO, reaction condition and the results are shown in Table 4.
Table 2
Comparative example 7-11:
The catalyst prepared in comparative example explanation employing comparative example is for the reactivity worth of hydrogenation VGO.
Catalyst D1-D5 comparative example prepared was at 800 DEG C, with 100% steam aging 12 hours, the cracking performance of miniature fixed fluidized bed ACE reaction unit to catalyst is used to evaluate respectively, the loadings of catalyst reactor is 9 grams, oil ratio is 4, reaction temperature is 500 DEG C, and weight (hourly) space velocity (WHSV) is 16h
-1, pass into hydrogenation VGO(as shown in table 3) to evaluate, steam consumption is 25 % by weight of hydrogenation VGO, reaction condition and the results are shown in Table 4.
Embodiment 20
According to the method Kaolinite Preparation of Catalyst of comparative example 6, unlike not adding y-type zeolite, and replace with the JK1 of equivalent, be designated as C8, evaluate according to the method for embodiment 12-19, evaluation result is in table 5.
Embodiment 21:
(1) in 15kg decationized Y sieve water, add the making beating of 7.5kg kaolin, then add 2.4kg boehmite, with hydrochloric acid, its pH value is adjusted to 2, stirs, stop stirring, at 70 DEG C, leave standstill aging 1 hour, add 3.6kg (with Al
2o
3meter) Alumina gel, stir, obtain alumina-clay slurries.
(2) in 15kg decationized Y sieve water, 6.0kg(butt is added) beta molecular sieve, 1.5kg(butt) ZRP-1 molecular sieve, 0.5kg(butt) (sodium oxide content is 0.2 % by weight to clinoptilolite, Si/A mol ratio=4.9) and 4.0kg(butt) obtained modification mesoporous Si-Al JK1, pull an oar 30 minutes, obtain the mixed serum of molecular sieve and modified mesoporous material, these slurries are joined in alumina-clay slurries prepared by above-mentioned steps (1), stir 0.5h, obtain catalyst slurry, by the slurries spray drying forming then will obtained, 500 DEG C of roastings 1.5 hours, obtain catalytic cracking catalyst C9.
(3) catalyst C9 is used for the reactivity worth of hydrogenation VGO, reaction condition and method are with embodiment 12-19, and reaction result is in table 5.
Table 3
Hydrogenation VGO shown in table 3 is obtained through hydrogenation by the VGO that reduces pressure, and the composition of decompression VGO is in table 3.
Hydroconversion condition: hydrogen dividing potential drop 8.5MPa, temperature 375 DEG C, NiMoW catalyst, hydrogen and oil volume compare 600:1.
Table 4
Table 5
From table 4 and table 5: catalyst aims hydrotreated feed provided by the invention oil has higher propylene and butylene productive rate, has higher isobutene productive rate, in liquefied gas propylene and isobutylene concentration higher, in gasoline aromatic hydrocarbons, BTX ratio is higher.In gasoline aromatic hydrocarbons, BTX ratio is high, is conducive to the cost reducing low-carbon alkene and aromatic hydrocarbons extraction and application.In addition, the virtue degree of bavin heavy oil (diesel oil and heavy oil) can be reduced, be conducive to the Cetane number improving diesel oil, can hold concurrently and produce lower pour point diesel oil.And bavin heavy oil quality can be improved, increase the ratio that mononuclear aromatics accounts for total aromatic hydrocarbons.From table 5, add a small amount of clinoptilolite, to raising liquefied gas yield, there is obvious effect, and propylene and butylene productive rate can be improved.
Embodiment 22
According to the method Kaolinite Preparation of Catalyst of embodiment 5, the content unlike JK1 is 35% weight, and the content of beta molecular sieve is the content of 10 % by weight, ZRP-1 molecular sieves is 5 % by weight, and the content of alumina binder is 30 % by weight, and the content of clay is 15 % by weight.
Embodiment 23
According to the method Kaolinite Preparation of Catalyst of embodiment 5, the content unlike JK1 is 5% weight, and the content of beta molecular sieve is the content of 40 % by weight, ZRP-1 molecular sieves is 20 % by weight, and the content of alumina binder is 10 % by weight, and the content of clay is 25 % by weight.
Claims (11)
1. transform for hydrotreatment oil the catalyst producing propylene and isobutene, described catalyst is primarily of the molecular sieve mixture composition of the heat-resistant inorganic oxide of 5-35 % by weight, the clay of 0-65 % by weight, the modification mesoporous silica-alumina materials of 5-50 % by weight and 15-60 % by weight; Wherein said molecular sieve mixture comprises beta molecular sieve and MFI molecular sieve, and described beta molecular sieve is not less than 1 with the ratio of the weight of MFI molecular sieve, and the weight ratio of described beta molecular sieve and described modification mesoporous silica-alumina materials is 1:5-5:1; Described modification mesoporous silica-alumina materials has boehmite crystal phase structure, and described modification mesoporous silica-alumina materials in the anhydrous expression formula of oxide weight is: (0-0.2) Na
2o (40-90) Al
2o
3(10-60) SiO
2; The specific area of described modification mesoporous silica-alumina materials is 200-400m
2/ g, pore volume are 0.5-2.0ml/g, average pore size is 5-25nm, most probable pore size is 5-15nm, described modification mesoporous silica-alumina materials is obtained by the method comprised the following steps: mixed with water by the mesoporous silica-alumina materials without ion-exchange and pull an oar, obtain slurries, again gained slurries and inorganic acid are contacted at least 0.2 hour at room temperature to 100 DEG C, make sodium oxide content in described mesoporous silica-alumina materials not higher than 0.2 % by weight, wherein, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:5-30:0.03-0.3.
2. according to catalyst according to claim 1, it is characterized in that, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:6-20:0.05-0.2.
3. according to catalyst according to claim 1, it is characterized in that, the weight ratio of the described mesoporous silica-alumina materials without ion-exchange, water and inorganic acid is 1:8-15:0.07-0.16.
4. according to the catalyst in claim 1-3 described in any one, it is characterized in that, the Contact Temperature of described slurries and inorganic acid is 30-80 DEG C, and time of contact is 0.2-2 hour.
5. according to the catalyst according to any one of claim 1-3, it is characterized in that, the preparation method of the described mesoporous silica-alumina materials without ion-exchange comprises: by during aluminium source and aqueous slkali are at room temperature to 85 DEG C and plastic, the pH of plastic terminal is 7-11; Then according to SiO
2: Al
2o
3=1:(0.6-9) weight ratio add silicon source, aging 1-10 hour at room temperature to 90 DEG C, then filters.
6., according to the catalyst in claim 1-3 described in any one, it is characterized in that, described without in the mesoporous silica-alumina materials of ion-exchange in the sodium content of sodium oxide molybdena for 0.5-15 % by weight.
7. according to catalyst according to claim 1, it is characterized in that, the weight ratio of described beta molecular sieve and described MFI molecular sieve is 2-9:1, and described two kinds of molecular sieve sums account for the 75-100 % by weight of molecular sieve mixture total amount, the weight ratio of described beta molecular sieve and described modification mesoporous silica-alumina materials is 1:3-3:1.
8. according to catalyst according to claim 1, it is characterized in that, described molecular sieve mixture comprises modenite and/or clinoptilolite, with the gross weight of molecular sieve mixture for benchmark, is no more than 25 % by weight in the content of the described clinoptilolite of butt and/or modenite; Described molecular sieve mixture does not comprise faujasite substantially.
9. according to catalyst according to claim 1, it is characterized in that, described MFI molecular sieve is ZRP molecular sieve and/or phosphorous and ZSM-5 molecular sieve that is transition metal, described beta molecular sieve is Hydrogen or for phosphorus and/or transition metal modified beta molecular sieve, described heat-resistant inorganic oxide comprise in aluminium oxide, silica, silica-alumina, phosphorous oxides, phosphorous oxide-aluminium oxide one or more.
10. the preparation method of the catalyst described in an any one of claim 1-9, comprise and described molecular sieve mixture, modification mesoporous silica-alumina materials, heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor are mixed, add or do not add clay, making beating, spray-dired step.
11. according to the preparation method of catalyst according to claim 10, and it is characterized in that, described preparation method is as follows:
1) the modification mesoporous silica-alumina materials described in preparation;
2) slurries comprising modification mesoporous silica-alumina materials, molecular sieve mixture and water are formed;
3) slurries comprising heat-resistant inorganic oxide and/or heat-resistant inorganic oxide precursor and/or clay are formed;
4) 3) add 2 in the slurries that obtain) slurries that obtain form catalyst slurry;
5) by step 4) the catalyst slurry spraying dry that obtains;
6) roasting.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147420A (en) * | 1995-10-06 | 1997-04-16 | 中国石油化工总公司 | Phosphorus and RE containing molecular sieve with MFI structure |
| CN1194181A (en) * | 1997-03-24 | 1998-09-30 | 中国石油化工总公司 | Phosphorus containing molecular sieve with MFI structure |
| CN1384173A (en) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | Cracking catalyst for paraffin-base oil material |
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN1854258A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Cracking catalyst |
| CN101362670A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method of propylene preparation |
| CN102430422A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing low-carbon olefin and application thereof |
-
2012
- 2012-06-25 CN CN201210213656.2A patent/CN103506152B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1147420A (en) * | 1995-10-06 | 1997-04-16 | 中国石油化工总公司 | Phosphorus and RE containing molecular sieve with MFI structure |
| CN1194181A (en) * | 1997-03-24 | 1998-09-30 | 中国石油化工总公司 | Phosphorus containing molecular sieve with MFI structure |
| CN1384173A (en) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | Cracking catalyst for paraffin-base oil material |
| CN1565733A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Process for preparing mesoporous Si-Al material and its preparing process |
| CN1854258A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Cracking catalyst |
| CN101362670A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method of propylene preparation |
| CN102430422A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic cracking catalyst for producing low-carbon olefin and application thereof |
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